International Journal of Advanced Research and Publications

ISSN: 2456-9992

Synthesis And Characterization Of Mesoporous

Silica Used As Catalyst In Biodiesel Production
Thin Thin Hlaing, Thar Htat Kyaw, Thida Kyaw, Min Min Htike
Department of Research and Innovation, Chemical Technology Research Center, Yangon, Myanmar, PH- 959 256 250 074
thinpa@gmail.com

Department of Research and Innovation, Chemical Technology Research Center, Yangon, Myanmar, PH- 959 795 578 954
tharhtatkyaw@gmail.com

Department of Research and Innovation, Chemical Technology Research Center, Yangon, Myanmar, PH- 959 430 115 53
dawthidakyaw.tdk@gmail.com

Department of Research and Innovation, Chemical Technology Research Center, Yangon, Myanmar, PH- 959 313 399 03
minnminnhtike.sbo@gmail.com

Abstract: Synthesis and characterization of silica nanoparticles were investigated. Cetyltrimethylammoniumbromide (CTAB) was used as
a templating agent for the preparation of mesoporous silica materials starting from sodium silicate solutions using a sol-gel method. Sodium
silicate was used as the silica source. The morphology and size of silica nanoparticles was characterized by powder X-ray diffraction
(XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM) and transmission electron microscope
(TEM). Amorphous silica nanoparticle was characterized by Wide Angle XRD. The SEM images of the silica nanoparticles are pherical like
aggregates was formed. But these samples have pore structure by TEM image and the size of nanoparticles is above 200 nm and the pore
size is in the range 2 to 50 nm. The synthesized silica nanoparticles were used as catalyst in Biodiesel production by tranesterification
method. The yield percentage of biodiesel produced by using silica nanoparticles is higher than without silica nanoparticles.

Keywords: Mesoporous, sol-gel, biodiesel, tranesterification

1. Introduction characteristic and electrical, magnetic or optical properties

SiO2 is ubiquitous in our environment; human exposure can
occur from natural or anthropogenic sources. Advancement
in nanotechnology in recent years has expanded the synthesis
of nonporous silica nanoparticles (SiNPs) for many
applications.[1] Silica particles with controllable porosity
have recently attracted much attention due to their excellent
optical, electrical and thermal properties and wide potential
applications in catalysis, separations, microelectronics, drug-
delivery systems, environmentally acceptable, structurally
stable, chemically resistant to organic solvents and microbial
attack and have high surface area and average pore size
between 2–50 nm. Ordered mesoporous silica were first
prepared by Yanagisawa et al.[2-3] Their large surface areas
allow for binding at a great number of active sites distributed
within the framework of these porous materials.[4] In
addition, this system can facilitate the diffusion of gas
molecules into pores in microporous systems [5], in which
pore-diffusion limitations influence the adsorption
equilibrium. A further benefit is often enhanced stability,
under both storage and operational conditions, e.g. towards
denaturation by heat or organic solvent. These are the
reasons for intensive studies of immobilization of various
enzymes onto mesoporous silica materials as supports [6 -
10]. Recently, major challenges for the preparation of
nanoparticle systems include development of new
compositions and the fabrication of multifunctional systems
with specific architectures. Thus, numerous particle systems
have been developed and fabricated by assembling diverse
nanoparticles on, encapsulated within, or integrated both
inside and on the surface of silica nanoparticles using
different synthesis methods. Properly coated or surface-
modified nanoparticles can offer a high potential for
numerous applications, due to change of their interfacial
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[11]. Thus, extensive research has been devoted to the
synthesis of core/shell particles. It is known that silica
particles synthesized by the Stöber method [12] Mesoporous
silica nanoparticles are usually synthesized by using
tetraethylorthosilicate (TEOS) as the silica source. However,
high cost of complex TEOS processing motivates the
development of alternative silica source [13]. In this study,
sodium silicate (Na2SiO3) and SiO2 were investigated to
synthesize mesoporous silica nanoparticles. It was also
conducted to determine the effects calcination temperature.
2. Research Material and Methods
2.1 Materials
CTAB (Cetyltrimethylammoniumbromide) were purchased
from BDH. Sodium silicate, sodium hydroxide,
orthophosphoric acid and other chemicals used in this
investigation, were purchased from commercial market.
3.2 Synthesis of Mesoporous Silica Nanoparticles
By using sol-gel method, sodium silicate was used as silica
source. Cetyltrimethyl ammoniumbromide (CTAB) was used
as template. Sodium silicate was first mixed with distilled
water to obtain an aqueous solution. CTAB was also
dissolved in water to obtain a clear solution. The two
solutions were then mixed stirred for 1 hr. The mixture had
the molar composition of 1.0 Na2 SiO3: 0.25 CTAB: 180
H2O. The pH value of the mixture was adjusted to pH 6.5 by
adding Orthophosphoric acid. The mixture was heated in
oven at 110˚C for 24 hr for crystallization. After the heating
process, the solid was recovered by centrifuge. The solid was
dried in oven overnight at 100˚C and then calcined in a
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ISSN: 2456-9992

furnace at 550˚C for 6 hr to decompose CTAB and to obtain
silica nanoparticles.
3.3 Characterization of Mesoporous Silica
Nanoparticles
The samples crystalline structure is characterized using X-ray
Diffraction (XRD) patterns using D8 ADVANCE
Diffractometer, BRUKER. The Field Emission Scanning
Electron Microscope (FESEM, Cross Beam Workstation)
was used to capture the images of sample. The electron
microscopy images of sample were taken on at acceleration
voltage of 5 kV and magnification of 34.51KX .The
morphologies of the synthesized nano silica were observed
by transmission electron microscopy (FEI-Tecnai G2/ F30S-
TWIN). Fourier Transform Infrared (FTIR) analysis of the
samples was carried out using Perkin Elmer Spectrum
spectrophotometer.
frequency band of the sample synthesized by sodium silicate
characterized using FTIR to identify the functional groups
present in those samples. Each peak is characteristic of a
specific functional group. The peaks ranging between 785
and 801 cm-1 are due to the Si-O-Si symmetric stretching
modes. The peaks located between 1063.05 and 1077.49 cm-
1
are apparent due to the asymmetric Si-O-Si stretching
modes. The silica from the sodium silicate on the surface of
the sample is evident from the frequency peaks detected.
(a)
(b)

3.4 Preparation of Biodiesel from Waste Cooking Oil

In biodiesel production, waste cooking oil, sodium hydroxide
and methanol were used. Silicon dioxide and silica
nanoparticles were used as catalyst. First is the filtration of
used oil and heating at 100˚C. Alcohol was mixed in the
Figure 2: FTIR of (a) SBA-15 and (b) Nanosilica prepared
molar ratio of alcohol/ oil 1:3. 0.1% Silica nanoparticles and
0.1% SiO2 was added respectively. 0.45% NaOH was also
The SEM image of the silica nanoparticles shows that
added and stirred at 60 ˚C about 2 hrs. The mixture was
spherical like aggregates was formed. The sample was
poured into the separating funnel and stood for overnight for
calcined for temperature 400°C, 500°C, 600°C, 700, 800°C.
the separation of biodiesel and glycerin. Then the biodiesel
As silicates aggregate easily, the SEM images of the sample
was washed by water at 60˚C about 6 times to clear
are not sharp and clear as shown in figure (3). Mesoporous
completely. Finally dry the biodiesel at 100˚C in oven to
structure of silica nanoparticles was also confirmed by TEM
remove moisture.
micrograph as it was shown in Figure (4). The samples have
pore structure by TEM image and the size of nanoparticles is
3.5 Measurement of Biodiesel Properties above 200 nm and the pore size is in the range 2 to 50 nm.
The extracted biodiesel was analyzed by Fourier Transform
Infrared (FTIR). The dynamic viscosity of the biodiesel was
measured by U- tube at 40˚C. Kinematic viscosity was also
calculated by using dynamic viscosity and density of the
extracted biodiesel. The flash point was measured by SETA
PM-93.

3. Result and Discussion

3.1 Synthesis and Characterization of Mesoporous silica
According to the XRD pattern, the silica nano samples are
amorphous silica as shown in Figure (1).
(a)

(b)

Figure 1: XRD pattern of silica prepared Figure 3: SEM Images of Silica Prepared Calcined
at (a) 500°C and (b) 600°C
The FTIR adsorption data was collected using the Perkin
Elmer Spectrum Spectrometer. Figure 2 displays the

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 International Journal of Advanced Research and Publications
ISSN: 2456-9992
Figure 4: TEM Images of Silica Prepared
3.2 Preparation and Measurement of Biodiesel
The biodiesel by producing with silica nanoparticles was
methyl linoleate according to FTIR result as shown in Figure
(5). The yield percentage of biodiesel by using silica
nanoparticles as catalyst was 95 % and it is higher than the
percentage of biodiesel without silica nanoparticles (84%).
The comparisons of the yield percentage of biodiesel are
shown in table (1) and Figure (6). The properties of biodiesel
with silica nanoparticles, commercial silica and without silica
are shown in Table (2). These are within the standard range
of biodiesel.
Figure 5: FTIR of Biodiesel Prepared
BF 1(without MSN) BF 2(with MSN) BF 3(with SiO )[7] Y.X. Bai, Y.F. Li, Y. Yang, L.X. Yi, “Covalent
2
Figure 6: Comparison of Yield Percentage of Biodiesel
Prepared BF-1, BF-2 and BF-3
4. Conclusions
Mesoporous silica was successfully synthesized under acidic
conditions using sodium silicate as the silica source. The
characterization showed that the materials are amorphous
silica nanoparticles and shape is spherical like aggregates
was formed. m2/g. The samples have pore structure by TEM
image and the size of nanoparticles is above 200 nm and the
pore size is in the range 2 to 50 nm. The catalytic activity
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toward transesterification of waste cooking oil with methanol
and sodium hydroxide showed difference among the using
commercial SiO2 and without silica. The synthesized
mesoporous silica showed the highest activity, with 95%
yield of biodiesel at 60°C. The other two commercial SiO2
and without silica yielded 78% and 80% biodiesel at the
same condition. The properties of biodiesel prepared with
mesoporous silica were within the standard reference range
of Biodiesel.
5. Acknowledgements
The authors would like to express the deepest gratitude to
Mr. Win Khaing Moe, Director General of Department of
Research and Innovation from Ministry of Education,
Yangon, Myanmar for providing research facility We would
thankful to Dr. Phyu Phyu Win Deputy Director General of
Department of Research and Innovation. Deeply thank to all
the members from Nano Chemical Technology Research
Division for co-operation and successful implementation of
research work.
References
[1] D. Das, Y. Yang et al., “Synthesis and Physicochemical
Characterization of Mesoporous SiO2 Nanoparticles,”
Journal of Nanomaterials, Volume 2014, Article ID
176015, 12 pgs, 2014.
[2] T. Yanagisawa, T. Shimizu, “The Preparation of
alkyltrimethylammonium-kanemite complexes and their
conversion to microporous materials,” Bulletin of the
Chemical Society of Japan, vol. 63(4), 988-992, 1990.
[3] D. Moelans, P. Cool, J Baeyens, E.F. Vansant, “Using
mesoporous silica materials to immobilize biocatalysis-
enzymes,” Catal. Comm., vol. 6, 307–311, 2005.
[4] M.A. Hernandez, J.A. Velasco, M. Asomoza,
“Adsorption of Benzene, toluene, and p-Xylene on
Microporous SiO2,” Industrial & Engineering Chemistry
Research, Vol. 43, 1779-1787, 2004.
[5] C. Knovel, J. Descarpentries, A. Benzaouia, V. Zelenak,
S. Mornet, P.L. Llewellyn, V. Hornebecq, Micropor.
Mesopor. Mater, Vol. 99, 79-85, 2007.
[6] Y. Wang, F. Caruso,“Enzyme encapsulation in
nanoporous silica spheres,” Chemical Communications,
Vol. 13, 1528–1729, 2004.
immobilization of triacylglycerol lipase onto
functionalized novel mesoporous silica supports,”
Journal of Biotechnology, vol. 125, 574–582, 2006.
[8] H. Takahashi, B. Li, T. Sasaki, C. Miyazaki, T. Kajino,
S. Inagaki, “Catalytic activity in organic solvents and
stability of immobilized enzymes depend on the pore
size and surface characteristics of mesoporous silica,”
Journal of Chemistry of Materials, Vol. 12, 3301–3305,
2000.
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[9] W. Na, Q. Wei, Z.C. Zou, Q.Y. Li, Z.R. Nie, “Large
pore 3D cubic mesoporous silica HOM-5 for enzyme
immobilization,” Journal of Materials Letters, Vol. 62,
3707–3709, 2008.

[10] D. Ma, M. Li, A.J. Patil, S. Mann, “Fabrication of

protein/silica core-shell nanoparticles by microemulsion
based molecular wrapping,” Advanced Materials,
Vol.16, 1838–1841, 2004.

[11] B.Y. Piao, A. Burns, J. Kim, U. Wiesner, “Designed

fabrication of silica-based nanostructured particle
systems for nanomedicine applications,” Advanced
Functional Materials, Vol- 18, 3745–3758, 2008.

[12] W. Stöber, A. Fink, E. Bohn, “Controlled growth of

monodisperse silica spheres in the micron size range,”
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68, 1968.

[13] Meléndez-Ortiz, H.I., Mercado-Silva, A., García-Cerda,

L.A., Castruita, G. and Perera-Mercado, Y.A. (2013)
“Hydrothermal synthesis of mesoporous silica MCM-41
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[14] Carlos A and Fabio E. Sierra, “Biodiesel Production

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Author Profile

Author 1 received the B.S. and M.S. degrees

in Medical Biotechnology from Yangon
Technological University in 2005 and 2007,
and Ph.D degrees in Medical Biotechnology
from Mandalay Technological University in
2011 respectively. During 2011-2015, she
worked as Principal Scientist in Biotechnology Research
Department (BRD), Ministry of Science and Technology of
Myanmar . She is working now as Principal Scientist in
Nanotechnology Research Division (NRD), Department of
Research and Innovation, Ministry of Education of Myanmar.

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International Journal of Advanced Research and Publications
ISSN: 2456-9992

Na2SiO3 + H2O CTAB + H2O

Stirring 30 min Stirring 30 min

Acidification (H3 PO4), pH 6.5

Stirring 60 min

Aqueous Solution

Dry at 110˚C @ Oven 24 hr

Crystallization

Washing

Wet Precipitation

Dry at 110˚C @ Oven, overnight

Calcined at 550˚C, 6hr

Mesoporous Silica nanoparticles

Flow Chart: Preparation of Mesoporous silica nanoparticles

Table 1: Comparison of Yield Percentage of Biodiesel Prepared BF-1, BF-2 and BF-3

MeOH Average Yield

Experiment WCO (ml) BF(ml)
(ml) (%)

BF-1 A 300 100 234 78

BF-1
(without silica) BF-1 B 300 100 260 86.7
BF-1 C 300 100 260 86.7
BF- 2 A 300 100 261 87
BF- 2
(with synthesized silica) BF- 2 B 300 100 285 95
BF- 2 C 300 100 270 90
BF- 3 A 300 100 240 80
BF – 3
( with commercial silica) BF- 3 B 300 100 235 78
BF- 3 C 300 100 250 83

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ISSN: 2456-9992

Table 2: Properties of Biodiesel Prepared BF-1, BF-2 and BF-3

Dynamic
Kinematic2Viscosity Density
3
Viscosity Flash Point
No. Experiments (mm / s) (g / m )
(cP or mPa.S) (˚C)
(at 40˚C) (at 24˚C)
(at 40˚C)

BF – 1
1. 5.38 6.163 0.873 166
(Without SiO2)
BF –2
2. 5.21 5.947 0.876 166
(With MSN)

BF – 3
3. 4.73 5.412 0.874 162
(With SiO )
2

4. Standard - 1.9 - 6 0.88 Above 160

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